CN110256622B - Reinforced and toughened syndiotactic polystyrene and preparation method thereof - Google Patents
Reinforced and toughened syndiotactic polystyrene and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a reinforcing and toughening syndiotactic polystyrene and a preparation method thereof, which are obtained by copolymerizing a styrene monomer modified by para-long-chain alkane and styrene; wherein the molar content of the para-long-chain alkane modified styrene structural unit in the copolymer is 0.5-20 mol%, and the long-chain alkane is composed of 9 or more carbon atoms; the microstructure of the strengthening and toughening syndiotactic polystyrene is syndiotactic. The invention utilizes the rare earth catalyst composition composed of rare earth compounds, organic boron salt and alkyl aluminum to catalyze the copolymerization of styrene monomer modified by para-long-chain alkane and styrene in an organic solution. The invention utilizes direct copolymerization method to introduce polyethylene chain segment into side chain of syndiotactic polystyrene, which can effectively improve toughness and strength, properly reduce melting temperature, and provide an effective solution for expanding application field of syndiotactic polystyrene and reducing difficulty of processing and forming process. Meanwhile, the preparation method is simple and feasible and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of polystyrene preparation, in particular to reinforced and toughened syndiotactic polystyrene and a preparation method thereof.
Background
Syndiotactic polystyrene is a new type of engineering plastic with high elastic modulus, high heat resistance, strong solvent and chemical reagent resistance, and high melting temperature up to 270 deg.C. The first use of the titanocene catalyst CpTiCl by Japanese Ishihara3First synthesis of MAO. However, the industrial and academic circles are troubled by the problems that syndiotactic polystyrene has large brittleness and a too narrow processing temperature window. In order to solve the drawbacks of syndiotactic polystyrene, researchers at the institute of physical and chemical sciences of Japan prepared syndiotactic ethylene-styrene copolymers having different ethylene contents by selectively and randomly copolymerizing styrene and ethylene in a syndiotactic manner using a single metallocene rare earth catalyst (J.Am.chem.Soc.2004,126, 13910-13911). Researchers at reyne university in france use a bis-cyclopentadienyl rare earth catalyst to catalyze the syndiotactic selective polymerization of ethylene and styrene to prepare a high syndiotactic ethylene-styrene copolymer (chem. eur. j.2007, 13, 5548). The researchers in the United states utilize the single metallocene titanium catalyst to realize the syndiotactic homopolymerization of styrene monomer modified by para-straight chain alkane (Macromolecules 2004,37, 3976-. German researchers used titanocene catalyst to catalyze p-butyl styrene andthe syndiotactic copolymerization of styrene monomer was found to have an effect on the crystalline morphology of syndiotactic polystyrene due to the introduction of para-butylstyrene. There is no literature on syndiotactic selective polymerization of para-long chain alkane modified styrene monomer and styrene, and there is no literature report on toughening and reinforcing syndiotactic polystyrene by using long chain alkane substituted styrene monomer.
Disclosure of Invention
The invention aims to provide reinforced and toughened syndiotactic polystyrene and a preparation method thereof, in particular to the reinforced and toughened syndiotactic polystyrene grafted by para-long-chain alkane. The invention prepares the enhanced and toughened syndiotactic polystyrene by directly copolymerizing the styrene monomer modified by the para-long-chain alkane and the styrene monomer, and has simple preparation process and easy regulation and control of the grafting density and the sequence distribution of the grafting density in the polymer.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides a reinforced and toughened syndiotactic polystyrene, which is obtained by copolymerizing a styrene monomer modified by para-long-chain alkane and styrene and has a segment shown in a formula (I):
in formula (I), 0.5 mol% < x/(x + y) <20 mol%; m is more than or equal to 7 and less than or equal to 49; n is more than or equal to 1000, x + y is less than or equal to 20000.
In the above technical solution, it is preferable that in formula (I), 1 mol% < x/(x + y) <15 mol%; m is more than or equal to 7 and less than or equal to 33; and n is more than or equal to 2000 and less than or equal to 15000.
In the above technical solution, it is further preferable that in formula (I), 1 mol% < x/(x + y) <10 mol%; m is more than or equal to 13 and less than or equal to 21; and n is more than or equal to 2000 and less than or equal to 10000 of x + y.
In the above technical solution, it is preferable that the polystyrene is syndiotactic, and the tacticity rrrr is greater than 95%.
In the above-mentioned embodiment, it is further preferable that the polystyrene is syndiotactic, and the tacticity rrrr is greater than 98%.
The invention also provides a preparation method of the reinforced and toughened syndiotactic polystyrene, which comprises the following steps:
under the anhydrous and anaerobic condition, adding the organic solution of the catalyst composition into the mixed solution of styrene and a styrene monomer modified by para-long chain alkane, and carrying out copolymerization to prepare the enhanced and toughened syndiotactic polystyrene in situ;
the reinforced and toughened syndiotactic polystyrene has a segment shown in a formula (I):
in formula (I), 0.5 mol% < x/(x + y) <20 mol%; m is more than or equal to 7 and less than or equal to 49; n is more than or equal to 1000 and x + y is less than or equal to 20000;
the para-long-chain alkane modified styrene monomer has a structure shown in a formula (II):
in the formula (II), m is more than or equal to 7 and less than or equal to 49;
the catalyst composition consists of a rare earth compound, an organic boron salt and alkyl aluminum.
In the above technical solution, preferably, the rare earth compound is a rare earth complex represented by formula (III) or a rare earth compound represented by formula (IV):
in formulae (III) and (IV):
X1and X2Independently cyclopentadiene and its derivatives, indene and its derivatives or fluorene and its derivatives;
Q1and Q2Each independently represents a monoanionic ligand;
R1selected from methylene or dimethylsilyl;
R2、R3、R4and R5Independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl;
l is a neutral Lewis base tetrahydrofuran, ethylene glycol dimethyl ether, pyridine or substituted pyridine;
w represents an integer of 0 to 2;
ln represents rare earth metal elements of scandium, yttrium, neodymium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
In the above technical solution, it is further preferable that:
X1is tetramethylcyclopentadiene, tetramethylphenylcyclopentadiene, pentamethylcyclopentadiene, tetramethyl (trimethylsilyl) cyclopentadiene, 1, 3-bis (trimethylsilyl) indene, 9-trimethylsilyl-fluorene or 9-trimethylsilyl-2, 7-di-tert-butylfluorene;
X2is tetramethyl cyclopentadiene, fluorene, 2, 7-di-tert-butyl fluorene or 3, 6-di-tert-butyl fluorene;
Q1and Q2Each independently is trimethylsilylmethylene, allyl, 2-methylallyl, tetramethylsilylamino, benzyl, 4-methylbenzyl or 2-N, N' -dimethylbenzyl;
R1is methylene;
R2、R3、R4and R5Are all hydrogen;
l is tetrahydrofuran;
w represents an integer of 0 to 2;
ln is scandium, yttrium, neodymium, gadolinium, holmium, erbium, thulium or lutetium.
In the above-mentioned aspect, it is preferable that the organoboron salt includes [ NHEt3][B(C6F5)4]、[Ph3C][B(C6F5)4]、B(C6F5)3And [ PhNMe2H][B(C6F5)4]One or more of; the alkyl aluminum is trimethyl aluminum, triethyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, triisobutyl aluminum, triisopropyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, and methylaluminoxaneAnd diisobutylaluminoxane.
In the technical scheme, the molar ratio of the sum of the para-long-chain alkane modified styrene monomer and the styrene monomer to the rare earth compound is preferably (1000-30000): 1; the mol ratio of the organic boron salt to the rare earth compound is (0.5-2): 1; the molar ratio of the alkyl aluminum to the rare earth compound is (1-500): 1; the temperature of the copolymerization is 20-130 ℃, and the time is 0.1-24 hours; the anhydrous and anaerobic condition is inert gas condition, specifically nitrogen and/or argon.
The invention has the beneficial effects that:
the invention provides a syndiotactic polystyrene with reinforced and toughened para long-chain alkane graft. The invention prepares the enhanced and toughened syndiotactic polystyrene by directly copolymerizing the styrene monomer modified by the para-long-chain alkane and the styrene monomer, and has simple preparation process and easy regulation and control of the grafting density and the sequence distribution of the grafting density in the polymer.
The invention also provides a preparation method of the reinforced and toughened syndiotactic polystyrene, which utilizes a catalyst composition consisting of a rare earth compound, an organic boron salt and alkyl aluminum to catalyze the copolymerization of a styrene monomer modified by long-chain alkane and styrene in an organic solution. The invention utilizes direct copolymerization method to introduce polyethylene chain segment into side chain of syndiotactic polystyrene, which can effectively improve toughness and strength, properly reduce melting temperature, and provide an effective solution for expanding application field of syndiotactic polystyrene and reducing difficulty of processing and forming process. Meanwhile, the preparation method is simple and feasible and is suitable for industrial production.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of reinforced and toughened syndiotactic polystyrene prepared in examples 1-7 of the present invention.
FIG. 2 is a graph of glass transition temperatures for reinforced toughened syndiotactic polystyrene prepared in examples 1-7 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts purity requirements which are conventional in the field of preparation of analytically pure or polyolefin materials.
The expression of the substituent in the present invention is not particularly limited, and the expression known to those skilled in the art is used, and the meaning of the substituent can be correctly understood by the expression based on the general knowledge of those skilled in the art.
All the raw materials of the invention, the marks or the abbreviations thereof belong to the conventional marks or the abbreviations thereof in the field, each mark and the abbreviation thereof are clear and definite in the field of related applications, and the technical personnel in the field can purchase the raw materials from the market or prepare the raw materials by the conventional method according to the marks, the abbreviations and the corresponding applications.
The invention provides a reinforced and toughened syndiotactic polystyrene, which is obtained by copolymerizing a para long-chain alkane modified styrene monomer and styrene, wherein the molar content of the para long-chain alkane modified styrene structural unit in the copolymer is 0.5-20 mol%; the alkane substituted styrene monomer para long-chain alkane is composed of 9 and more than 9 carbon atoms; the microstructure of the strengthening and toughening syndiotactic polystyrene is syndiotactic and has a segment shown in a formula (I):
in formula (I):
the molar content of the para-long-chain alkane modified styrene structural unit is 0.5 mol% < x/(x + y) <20 mol%; preferably 1 mol% < x/(x + y) <15 mol%; more preferably 1 mol% < x/(x + y) <10 mol%;
the number of side chain carbon atoms 49 of the para-long-chain alkane modified styrene structural unit is more than or equal to m and more than or equal to 7; preferably 7. ltoreq. m. ltoreq.33; more preferably 13. ltoreq. m.ltoreq.21;
the total number of the repeating structural units in the reinforced and toughened syndiotactic polystyrene is not less than 1000, and n is not less than x + y is not less than 20000; preferably 2000 ≦ n ≦ x + y ≦ 15000; more preferably 2000 ≦ n ≦ x + y ≦ 10000.
The styrene structural unit and the para long-chain alkane modified styrene structural unit are both syndiotactic;
said polystyrene is syndiotactic, preferably having a tacticity rrrr > 95%; more preferably the tacticity rrrr is > 98%.
The invention also provides a preparation method of the reinforced and toughened syndiotactic polystyrene, which comprises the following steps:
under the anhydrous and anaerobic condition, adding the organic solution of the catalyst composition into the mixed solution of styrene and a styrene monomer modified by para-long chain alkane, and carrying out copolymerization to prepare the enhanced and toughened syndiotactic polystyrene in situ;
the reinforced and toughened syndiotactic polystyrene has a segment shown in a formula (I):
in formula (I), 0.5 mol% < x/(x + y) <20 mol%; m is more than or equal to 7 and less than or equal to 49; n is more than or equal to 1000, x + y is less than or equal to 20000.
The para-long-chain alkane modified styrene monomer has a structure shown in a formula (II):
in the formula (II), m is more than or equal to 7 and less than or equal to 49;
the catalyst composition consists of a rare earth compound, an organic boron salt and alkyl aluminum.
The preparation method of the catalyst composition comprises the steps of respectively dissolving a rare earth compound and an organic boron salt in an organic solvent under an inert atmosphere, slowly pouring an organic solution of the organic boron salt into an organic solution of the rare earth compound, reacting for a certain time, and adding a main group alkyl reagent alkyl aluminum into the mixed solution to obtain the organic solution of the rare earth catalyst composition.
In the preparation method of the reinforced and toughened syndiotactic polystyrene, the styrene monomer modified by the para-long-chain alkane and the styrene monomer are preferably dissolved in an organic solvent under inert gas, and then are added into a polymerization reaction device. After setting polymerization reaction conditions, adding an organic solution of the catalyst composition, starting the polymerization reaction, adding ethanol with an anti-aging agent to terminate the polymerization reaction after presetting polymerization time, settling the polymer, and then pumping out volatile matters in a vacuum oven to obtain a target product.
In the above preparation method of the present invention, the selection of the structure and the substituent of the material or raw material and the preferred range thereof are consistent with the selection of the structure and the substituent of the reinforced and toughened syndiotactic polystyrene and the preferred range thereof, and are not repeated herein.
The conditions of the present invention for the anhydrous and oxygen-free are not particularly limited, and may be oxygen-free conditions well known to those skilled in the art, and those skilled in the art can select the conditions according to actual production conditions, product properties and quality requirements, and the oxygen-free conditions of the present invention are more preferably water-free and oxygen-free conditions.
The mode of generating the anhydrous and anaerobic conditions is not particularly limited in the present invention, and may be generated by conventional methods well known to those skilled in the art, and those skilled in the art can select the anhydrous and anaerobic conditions according to actual production conditions, product performance and quality requirements, and the mode of generating the anhydrous and anaerobic conditions preferably includes introducing a protective gas. The protective gas is not particularly limited in the present invention, and may be any protective gas known to those skilled in the art, and those skilled in the art can select the protective gas according to actual production conditions, product performance and quality requirements, and the protective gas preferably includes nitrogen and/or inert gas, more preferably nitrogen or argon, and most preferably nitrogen.
The copolymerization mode in the present invention is not particularly limited, and those skilled in the art can select the copolymerization mode according to the actual production situation, product performance and quality requirements, and the copolymerization in the present invention is preferably solution polymerization, i.e. polymerization reaction in the presence of organic solvent.
The organic solvent is not particularly limited in the present invention, and may be any conventional organic solvent known to those skilled in the art, and those skilled in the art can select the organic solvent according to actual production conditions, product properties and quality requirements, and the organic solvent in the present invention preferably includes one or more of saturated alkane, aromatic hydrocarbon, halogenated alkane, halogenated aromatic hydrocarbon and naphthenic organic solvent, and more preferably one or more of saturated alkane, aromatic hydrocarbon, halogenated alkane, halogenated aromatic hydrocarbon and naphthenic organic solvent. Specifically, the solvent preferably includes one or more of n-hexane, n-heptane, petroleum ether, cyclohexane, methylcyclohexane, decahydronaphthalene, ethylbenzene, toluene, xylene, chlorobenzene, dichlorobenzene, bromobenzene and dichloromethane, and more preferably n-hexane, decahydronaphthalene, petroleum ether, cyclohexane, methylcyclohexane, toluene or chlorobenzene; more preferably one or more of n-hexane, decalin, petroleum ether, cyclohexane and toluene.
The temperature for the copolymerization is not particularly limited, and may be a conventional copolymerization temperature well known to those skilled in the art, and those skilled in the art may select the temperature according to actual production conditions, product performance and quality requirements, and the temperature for the copolymerization in the present invention is preferably 20 to 130 ℃, more preferably 50 to 130 ℃, and most preferably 70 to 130 ℃.
The copolymerization time is not particularly limited, and can be conventional copolymerization time known by a person skilled in the art, and the person skilled in the art can select the copolymerization time according to the actual production situation, product performance and quality requirements, and the copolymerization time in the invention is preferably 0.10-24 hours, more preferably 1-10 hours, and most preferably 3-10 hours.
The amount of the styrene monomer added in the present invention is not particularly limited, and may be any amount conventionally added as is well known to those skilled in the art, and those skilled in the art can select the amount according to actual production conditions, product properties and quality requirements.
The addition amount of the para-long chain alkane modified styrene monomer is not particularly limited in the present invention, and can be selected by those skilled in the art according to actual production conditions, product performance and quality requirements. The insertion rate of the para-long-chain alkane modified styrene monomer in the reinforced and toughened syndiotactic polystyrene is 0.5-20 mol%.
Preferably, the molar ratio of the sum of the para-long-chain alkane modified styrene monomer and the styrene monomer to the rare earth compound is (1000-30000): 1.
The preparation of the catalyst composition is not particularly limited, and a person skilled in the art can select the catalyst composition according to the actual production condition, the product performance and the quality requirement.
Preferably, the rare earth compound of the invention is a rare earth complex shown in formula (III) or a rare earth compound shown in formula (IV):
wherein, X1Cyclopentadiene and its derivatives, indene and its derivatives or fluorene and its derivatives; preferably tetramethylcyclopentadiene, tetramethylphenylcyclopentadiene, pentamethylcyclopentadiene, pentaphenylcyclopentadiene, tetraphenylcyclopentadiene, pentaethylcyclopentadiene, tetramethyl (trimethylsilyl) cyclopentadiene, 1, 4-di-tert-butylpyrrole, tetramethyl (phenyldimethylsilyl) cyclopentadiene, 1, 3-bis (trimethylsilyl) indene, 1, 3-bis (trimethylsilyl) -2-methylindene, 9-trimethylsilylfluorene, 9-trimethylsilyl2, 7-di-tert-butylfluorene or 9-trimethylsilyl-3, 6-di-tert-butylfluorene; more preferably tetramethylcyclopentadiene, tetramethylphenylcyclopentadiene and pentamethylcyclopentadieneDiene, tetramethyl (trimethylsilyl) cyclopentadiene, 1, 4-di-tert-butylpyrrole, 1, 3-bis (trimethylsilyl) indene, 1, 3-bis (trimethylsilyl) -2-methylindene, 9-trimethylsilyl-fluorene, 9-trimethylsilyl-2, 7-di-tert-butylfluorene or 9-trimethylsilyl-3, 6-di-tert-butylfluorene; more preferably tetramethylcyclopentadiene, tetramethylphenylcyclopentadiene, pentamethylcyclopentadiene, tetramethyl (trimethylsilyl) cyclopentadiene, 1, 3-bis (trimethylsilyl) indene, 9-trimethylsilyl-fluorene or 9-trimethylsilyl-2, 7-di-tert-butylfluorene.
X2Cyclopentadiene and its derivatives, indene and its derivatives or fluorene and its derivatives; preferably tetramethylcyclopentadiene, fluorene, 2, 7-di-tert-butylfluorene or 3, 6-di-tert-butylfluorene.
Q1And Q2Each independently represents a monoanionic ligand, preferably an alkyl group, a silane group, an amine group, a silicon amine group, an arylamine group, an allyl group, an aryl group, a boron hydride group, a tetramethylaluminum group, hydrogen, chlorine, bromine, or iodine; more preferably each independently is trimethylsilylmethylene, bistrimethylsilyloxymethylene, allyl, 2-methylallyl, 1, 3-bistrimethylsilylallyl, hexamethylsilylamine, tetramethylsilylamine, methyl, benzyl, 4-methylbenzyl, 2-N, N' -dimethylbenzyl, tetramethylaluminum, borohydride, hydrogen, chlorine or bromine; still more preferably trimethylsilylene, allyl, 2-methylallyl, hexamethylsilylamine, tetramethylsilylamine, benzyl, 4-methylbenzyl, 2-N, N '-dimethylbenzyl, tetramethylaluminum or chlorine, and most preferably trimethylsilylene, allyl, 2-methylallyl, tetramethylsilylamine, benzyl, 4-methylbenzyl or 2-N, N' -dimethylbenzyl.
R1Selected from methylene or dimethylsilyl; methylene is preferred.
R2、R3、R4And R5Independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl; preferred R2、R3、R4And R5Are all hydrogen.
L is a neutral Lewis base tetrahydrofuran, ethylene glycol dimethyl ether, pyridine or substituted pyridine; tetrahydrofuran is preferred.
w represents an integer of 0 to 2;
ln represents rare earth metal elements such as scandium, yttrium, neodymium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium; still more preferred is scandium, yttrium, neodymium, gadolinium, holmium, erbium, thulium or lutetium.
The specific structure of the rare earth compound is not particularly limited, and a person skilled in the art can select and adjust the structure according to the actual application condition, the product performance and the quality requirement, and the rare earth complex can be specifically the following complex:
the alkyl aluminum in the present invention is preferably one or more of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri-n-butyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminum hydride, dipentyl aluminum hydride, dihexyl aluminum hydride, dioctyl aluminum hydride, dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dipentyl aluminum chloride, dihexyl aluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, methylaluminoxane (MAO, DMAO, MMAO), ethylaluminoxane, n-propyl aluminoxane, isobutyl aluminoxane, and n-butyl aluminoxane; preferably one or more of trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisobutylaluminum, triisopropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, methylaluminoxane and diisobutylaluminoxane;
the organic boron salt is not particularly limited in the present invention, and may be any organic boron salt known to those skilled in the art for use in rare earth catalyst compositions, and those skilled in the art can select the organic boron salt according to actual production conditions, product properties and quality requirementsIn order to improve the catalytic efficiency and ensure the performance of the product, the organic boron salt contains [ B (C)6F5)4]–And/or B (C)6F5)3(ii) a Preferably, the organoboron salt comprises [ NHEt3][B(C6F5)4]、[Ph3C][B(C6F5)4]、B(C6F5)3And [ PhNMe2H][B(C6F5)4]One or more of;
the adding amount of the organic boron salt is not particularly limited, and can be selected by the skilled in the art according to the actual production situation, the product performance and the quality requirement, and the mol ratio of the organic boron salt to the rare earth complex is preferably (0.5-2): 1, more preferably (1.0 to 2.0): 1, specifically 1: 1.
the adding amount of the aluminum alkyl is not particularly limited, and the conventional adding amount for the rare earth catalyst composition known by the skilled in the art can be used, the skilled in the art can select the adding amount according to the actual production situation, the product performance and the quality requirement, and the molar ratio of the aluminum alkyl to the rare earth compound is preferably (1-500): 1, more preferably (10 to 300): 1, more preferably (20 to 200): 1, most preferably (40-100): 1.
to further illustrate the present invention, a reinforced and toughened syndiotactic polystyrene and a method for preparing the same are described in detail with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and that the detailed embodiments and specific procedures are given only for further illustrating the features and advantages of the present invention, not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
The present invention is not particularly limited with respect to the sources of the raw materials in the following examples, and they may be prepared by a preparation method known to those skilled in the art or commercially available.
Example 1
Under the anhydrous and oxygen-free conditions, 10 mu mol [ Ph ]3C][B(C6F5)4]1mL of the solution was poured into 2mL of a toluene solution of 10. mu. mol of a rare earth compound 2c, and 200. mu. mol of AiiBu was added3A toluene solution of the catalyst composition was prepared. The toluene solution of the catalyst composition was added to 3 ml of a toluene solution containing 2.062g of a styrene monomer (19.8mmol) and 0.0741g of a p-nonaalkylstyrene monomer (0.2mmol), reacted at 25 ℃ for 1 hour, then added with an ethanol solution containing an antioxidant to terminate the polymerization reaction, and the polymer obtained by the precipitation was dried in a vacuum oven at 50 ℃ for 48 hours to obtain the target product. The polymer had a molar content of p-nonaalkylstyrene structural units of about 1.0% and a number average molecular weight of 28.7X 104The molecular weight distribution was 2.02, the glass transition temperature was 91 ℃ and the melting temperature was 257 ℃.
Examples 2 to 12: the experimental procedure of this series of examples is the same as in example 1, the polymerization conditions and the variation of the catalytic system and the polymerization results are detailed in the table below.
The polymerization conditions were: the dosage of the rare earth compound is 10 mu mol, [ Ln]:[Ph3C][B(C6F5)4]:[AliBu3]1:1:20(mol/mol/mol), concentration of monomer in toluene solution 2mol/L, [ a]High temperature GPC: the measured values were obtained using polystyrene as a standard and 1,2, 4-trichlorobenzene as an eluent at 150 ℃. [ b ] a]Measured by DSC, the temperature rise rate was 10 ℃/min after the heat history was removed. c polymerization conditions are [ Ln]:[Ph3C][B(C6F5)4]:[AliBu3]1:1:40 (molar ratio). [ d]Polymerization conditions are [ Ln]:[Ph3C][B(C6F5)4]:[AliBu3]1:1:100 (molar ratio). Ln represents a rare earth compound central metal. [ M ] A]Represents a para-long-chain alkane modificationThe sum of the moles of the modified styrene monomer and styrene monomer.
The enhanced and toughened syndiotactic polystyrenes prepared in examples 1 to 7 of the present invention were subjected to nuclear magnetic resonance hydrogen spectroscopy (see FIG. 1). The nmr hydrogen spectra were obtained for the samples in example 7, example 6, example 5, example 4, example 3, example 2, and example 1 in this order from top to bottom. Nuclear magnetic resonance hydrogen spectrum test the deuterated reagent is deuterated o-dichlorobenzene tested at 100 ℃.
FIG. 2 is a graph of glass transition temperatures for inventive examples 1,2, 3, 4, 5, 6 and 7. The curve is measured in a nitrogen atmosphere at a temperature increase/decrease speed of 10/min after the thermal history is eliminated. As can be seen from FIG. 2, the glass transition temperature of the copolymer prepared by the present invention is closely related to the alkyl chain length of the substituent group.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (6)
1. The reinforced and toughened syndiotactic polystyrene is characterized in that the syndiotactic polystyrene is obtained by copolymerizing a styrene monomer modified by para-long-chain alkane with styrene and has a segment shown in a formula (I):
in formula (I), 1 mol% < x/(x + y) <10 mol%; m is more than or equal to 13 and less than or equal to 33; n is equal to or more than 2000 and x + y is equal to or less than 10000;
the polystyrene is syndiotactic with a tacticity rrrr > 98%.
2. The method for preparing the reinforced and toughened syndiotactic polystyrene as claimed in claim 1, wherein the method comprises the following steps:
under the anhydrous and anaerobic condition, adding the organic solution of the catalyst composition into the mixed solution of styrene and a styrene monomer modified by para-long chain alkane, and carrying out copolymerization to prepare the enhanced and toughened syndiotactic polystyrene in situ;
the reinforced and toughened syndiotactic polystyrene has a segment shown in a formula (I):
in formula (I), 1 mol% < x/(x + y) <10 mol%; m is more than or equal to 13 and less than or equal to 33; n is equal to or more than 2000 and x + y is equal to or less than 10000;
the para-long-chain alkane modified styrene monomer has a structure shown in a formula (II):
in the formula (II), m is more than or equal to 13 and less than or equal to 33;
the catalyst composition consists of a rare earth compound, an organic boron salt and alkyl aluminum.
3. The method for preparing the reinforced and toughened syndiotactic polystyrene as claimed in claim 2, wherein said rare earth compound is a rare earth complex represented by formula (III) or a rare earth compound represented by formula (IV):
in formulae (III) and (IV):
X1and X2Independently cyclopentadiene and its derivatives, indene and its derivatives or fluorene and its derivatives;
Q1and Q2Each independently represents a monoanionic ligand;
R1selected from methylene or dimethylA silicon-based group;
R2、R3、R4and R5Independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl;
l is a neutral Lewis base tetrahydrofuran, ethylene glycol dimethyl ether, pyridine or substituted pyridine;
w represents an integer of 0 to 2;
ln represents rare earth metal elements of scandium, yttrium, neodymium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
4. The method for preparing reinforced and toughened syndiotactic polystyrene as claimed in claim 3,
X1is tetramethylcyclopentadiene, tetramethylphenylcyclopentadiene, pentamethylcyclopentadiene, tetramethyl (trimethylsilyl) cyclopentadiene, 1, 3-bis (trimethylsilyl) indene, 9-trimethylsilyl-fluorene or 9-trimethylsilyl-2, 7-di-tert-butylfluorene;
X2is tetramethyl cyclopentadiene, fluorene, 2, 7-di-tert-butyl fluorene or 3, 6-di-tert-butyl fluorene;
Q1and Q2Each independently is trimethylsilylmethylene, allyl, 2-methylallyl, tetramethylsilylamino, benzyl, 4-methylbenzyl or 2-N, N' -dimethylbenzyl;
R1is methylene;
R2、R3、R4and R5Are all hydrogen;
l is tetrahydrofuran;
w represents an integer of 0 to 2;
ln is scandium, yttrium, neodymium, gadolinium, holmium, erbium, thulium or lutetium.
5. The method for preparing reinforced and toughened syndiotactic polystyrene as claimed in claim 2,
the organoboron salt includes [ NHEt3][B(C6F5)4]、[Ph3C][B(C6F5)4]、B(C6F5)3And [ PhNMe2H][B(C6F5)4]One or more of;
the alkyl aluminum is: one or more of trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-propylaluminum, triisobutylaluminum, triisopropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, methylaluminoxane and diisobutylaluminoxane.
6. The method for preparing reinforced and toughened syndiotactic polystyrene as claimed in claim 2,
the molar ratio of the sum of the para-long-chain alkane modified styrene monomer and the styrene monomer to the rare earth compound is (1000-30000): 1;
the mol ratio of the organic boron salt to the rare earth compound is (0.5-2): 1;
the molar ratio of the alkyl aluminum to the rare earth compound is (1-500): 1;
the temperature of the copolymerization is 20-130 ℃, and the time is 0.1-24 hours; the anhydrous and anaerobic condition is inert gas condition, specifically nitrogen and/or argon.
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| CN105440187A (en) * | 2014-08-14 | 2016-03-30 | 中国科学院长春应用化学研究所 | Functional highly-syndiotactic polystyrene and preparation method thereof |
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